Hot-melt adhesive compositions comprising acidic polymer and basic polymer blends

ABSTRACT

A hot-melt adhesive composition comprises a blend of at least one acidic polymer and at least one basic polymer. At least one of the polymers is a hot-melt adhesive. Thermally reversible crosslinks are formed between each of the two polymers. These crosslinks impart cohesive strength to the applied adhesive, without sacrificing ease of processing.

FIELD OF THE INVENTION

The present invention relates to hot-melt adhesive compositions. Inparticular, hot-melt adhesive blends and methods for their preparationand use are taught by the present invention.

BACKGROUND OF THE INVENTION

Adhesives are often characterized by the form in which they are providedfor application. Traditionally, adhesives have been provided in organicsolvent for subsequent application. Such adhesives are applied to asubstrate and the solvent is then removed. Hot-melt adhesivesadvantageously reduce or eliminate the use of organic solvents inadhesives and their processing. Hot-melt adhesive systems areessentially 100% solid systems. Usually, such systems have no more thanabout 5% organic solvents or water, more typically no more than about 3%organic solvents or water. Most typically, such systems are free oforganic solvents and water. Advantageously, by reducing the use oforganic solvents, special handling concerns associated therewith arealso reduced.

Among hot-melt adhesive chemistries, (meth)acrylates (i.e.,methacrylates and acrylates) are one of the most prominent.(Meth)acrylates have evolved as a preferred class of adhesives due totheir clarity, permanence of properties over time, and versatility ofadhesion, to name just a few of the their benefits.

Hot-melt adhesives have a sufficient viscosity upon melting, such thatthey can be hot-melt processed (e.g., applied to a substrate). Byadjusting the processing temperature, the viscosity of the adhesive canbe readily tailored for application. For high performance applications(i.e., those requiring relatively strong cohesion, such as shear holdingstrength), some method of increasing the cohesive strength of appliedhot-melt adhesives is often needed (e.g., post-crosslinking ormoisture-curing).

For example, energy sources, such as electron beam (e-beam) orultraviolet (UV) radiation, are commonly used to crosslink adhesivesafter application. These methods, however, often require an additionalprocessing step and, thus, result in decreased processing efficiency.Furthermore, e-beam is not always desired because it is expensive andcan cause damage to some backings when the adhesive is used in a tape.Similarly, UV-radiation has its limitations as a crosslinking energysource. For example, UV-radiation is often not able to be usedeffectively for crosslinking relatively thick adhesives due to the needfor UV-radiation to penetrate throughout the entire thickness of theadhesive. As such, certain fillers and pigments can not be used inadhesives when UV-crosslinking is used because they potentiallyinterfere with penetration of UV-radiation therethrough.

One way to improve cohesive strength of an adhesive is by chemicalcrosslinking. Such crosslinking involves chemically bridging at leasttwo polymer chains together through bonds (e.g., covalent and ionicbonds). To promote ionic crosslinking, ionic crosslinking agents havebeen explored. To date, most ionic crosslinking agents include inorganicmetal additives. Further detail of particular chemically crosslinkedadhesives is provided below.

For example, Japanese Laid-Open Patent Application (Kokai) 54-88,938 toToyo Ink Mfg. KK discloses a hot-melt adhesive composition comprising acopolymer of a carboxylic acid and a (meth)acrylate and a polymer of anamine compound having an ethylenically unsaturated bond. The aminecompounds are used individually or in combination of two or more thereofin a polymer obtained by polymerizing the amine compounds. The aminecompound may also be copolymerized with monomers in the carboxylicacid/(meth)acrylate copolymer. It is stated, however, that in thissituation, the kind and composition of the amine compound must becarefully controlled so that the resulting copolymer can have both goodadhesive strength and good cohesive strength. Furthermore, theproduction process is liable to be complicated.

Everaerts et al. (U.S. Pat. No. 5,612,136) disclose adhesives comprisinga crosslinked copolymer of certain (meth)acrylate esters, certainnitrogen containing basic monomers copolymerizable therewith, optionalcopolymerizable acidic monomer, and crosslinker.

Lohmann (PCT Publication No. WO 96/05813) teaches preparation of apressure-sensitive adhesive film having a pressure-sensitive adhesivepolyacrylate copolymer with at least 3 mole-% of co-polymerized acrylicacid or methacrylic acid, a polymer containing a basic amino group, anda plasticizer. Exemplified pressure-sensitive adhesives are preparedusing organic solvents and coated out of an organic solvent-ethanol.

Guerin et al. (U.S. Pat. No. 4,152,189) disclose polyacrylic hot-meltadhesives prepared by blending from 5 to 95 parts by weight of a firstcopolymer with from 5 to 95 parts by weight of a second copolymer. Eachof the copolymers comprises 0.5 to 15 parts by weight of anethylenically unsaturated amine, carboxylic acid or sulfonic acid ormixtures thereof.

Desired hot-melt adhesives are those that have the ability to betailored for a myriad of diverse applications. It is also desired thatsuch hot-melt adhesives are able to meet cohesive strength requirementsof certain applications without compromising processing efficiency ortailorability.

SUMMARY OF THE INVENTION

Hot-melt adhesives of the present invention comprise a blend of at leastone acidic polymer and at least one basic polymer. Preferably, at leastone of the acidic polymer and the basic polymer has hot-melt adhesiveproperties. Preferably, at least one of the acidic polymer and the basicpolymer is a copolymer. Thermally reversible chemical crosslinks allowthe adhesive to be easily hot-melt processed, but provide improvedcohesive strength to the hot-melt adhesive after its application andcooling.

The acidic polymer is derived from at least one acidic monomer.Preferably, the acidic monomer is selected from ethylenicallyunsaturated carboxylic acids, ethylenically unsaturated sulfonic acids,ethylenically unsaturated phosphonic acids, and mixtures thereof. Due totheir availability, particularly preferred acidic monomers are theethylenically unsaturated carboxylic acids. When even stronger acids aredesired, particularly preferred acidic monomers include theethylenically unsaturated sulfonic acids and ethylenically unsaturatedphosphonic acids.

Preferably, the acidic polymer is a copolymer derived from at least oneacidic monomer and at least one non-acidic copolymerizable monomer. Inparticular embodiments, such acidic copolymers have hot-melt adhesiveproperties (e.g., pressure-sensitive hot-melt adhesive properties orheat-activatable hot-melt adhesive properties). Other monomers can becopolymerized with the acidic monomers (e.g., basic monomers, vinylmonomers, and (meth)acrylate monomers) as long as the acidic copolymerretains its acidity (i.e., it can still be titrated with a base). Morepreferably, however, the copolymerizable monomers are essentially freeof basic monomers (i.e., the copolymerizable monomers include about 5wt. % or less of basic monomers, but most preferably, thecopolymerizable monomers are free of basic monomers).

Most preferably, the acidic polymer is an acidic (meth)acrylatecopolymer. In this embodiment, the acidic (meth)acrylate copolymer isderived from at least one acidic monomer and at least one (meth)acrylatemonomer selected from the group consisting of monofunctional unsaturated(meth)acrylate esters of non-tertiary alkyl alcohols, and mixturesthereof, the alkyl groups of which comprise from about 1 to about 20carbon atoms, preferably about 1 to about 18 carbon atoms, such as thoseof Formula (I):

wherein R¹ is H or CH₃, the latter corresponding to where the(meth)acrylate monomer is a methacrylate monomer, and R² is a linear,branched, aromatic, or cyclic hydrocarbon group.

The basic polymer is derived from at least one basic monomer. Preferredbasic monomers are non-nucleophilic amine-functional monomers, such asthose of Formula (II):

wherein

a is 0 or 1;

R is selected from H— and CH₃—,

X is selected from —O—and —NH—;

Y is a divalent linking group, preferably comprising about 1 to about 5carbon atoms for ease of availability; and

Am is a tertiary amine fragment, such as the group:

wherein R¹ and R² are selected from alkyl, aryl, cycloalkyl, and arenylgroups. R¹ and R² in the above group may also form a heterocycle.Alternatively, Am can be pyridinyl or imidazolyl, substituted orunsubstituted. In all embodiments, Y, R¹, and R² may also compriseheteroatoms, such as O, S, N, etc.

Exemplary basic monomers include N,N-dimethylaminopropyl methacrylamide(DMAPMAm); N,N-diethylaminopropyl methacrylamide (DEAPMAm);N,N-dimethylaminoethyl acrylate (DMAEA); N,N-diethylaminoethyl acrylate(DEAEA); N,N-dimethylaminopropyl acrylate (DMAPA);N,N-diethylaminopropyl acrylate (DEAPA); N,N-dimethylaminoethylmethacrylate (DMAEMA); N,N-diethylaminoethyl methacrylate (DEAEMA);N,N-dimethylaminoethyl acrylamide (DMAEAm); N,N-dimethylaminoethylmethacrylamide (DMAEMAm); N,N-diethylaminoethyl acrylamide (DEAEAm);N,N-diethylaminoethyl methacrylamide (DEAEMAm); N,N-dimethylaminoethylvinyl ether (DMAEVE); N,N-diethylaminoethyl vinyl ether (DEAEVE); andmixtures thereof. Other useful basic monomers include vinylpyridine,vinylimidazole, tertiary amino-functionalized styrene (e.g.,4-(N,N-dimethylamino)-styrene (DMAS), 4-(N,N-dimethylamino)-styrene(DEAS)), and mixtures thereof.

Preferably, the basic polymer is a copolymer derived from at least onebasic monomer and at least one non-basic copolymerizable monomer. Inparticular embodiments, such basic copolymers have hot-melt adhesiveproperties (e.g., pressure-sensitive hot-melt adhesive properties orheat-activatable hot-melt adhesive properties). Other monomers can becopolymerized with the basic monomers (e.g., acidic monomers, vinylmonomers, and (meth)acrylate monomers), as long as the basic copolymerretains its basicity (i.e., it can still be titrated with an acid). Mostpreferably, however, the copolymerizable monomers are essentially freeof acidic monomers (i.e., the copolymerizable monomers include about 5wt. % or less of acidic monomers, but most preferably, thecopolymerizable monomers are free of acidic monomers).

Preferably, the basic copolymer is a basic (meth)acrylate copolymer. Inthis embodiment, the basic (meth)acrylate copolymer is derived from atleast one monomer of Formula I.

In one embodiment, the hot-melt adhesive composition comprises a blendof:

an acidic copolymer derived from a first group of monomers comprising atleast one acidic monomer; and

a basic copolymer derived from a second group of monomers comprising atleast one basic monomer,

wherein at least one of the first and second group of monomers comprisesgreater than about 15% by weight of acidic or basic monomers,respectively. That is, the acidic copolymer is derived from at least 15%by weight of acidic monomers and/or the basic copolymer is derived fromat least 15% by weight of basic monomers, based on total weight of therespective monomers. Preferably, at least one of the first and secondgroup of monomers comprises at least about 25% by weight, morepreferably at least about 35% by weight, even more preferably at leastabout 50% by weight, and most preferably at least about 60% by weight ofthe respective acidic or basic monomers. Preferably, each of the acidiccopolymer and the basic copolymer is derived from monomers comprising atleast one (meth)acrylate monomer, most preferably an alkyl(meth)acrylate monomer. Although more may be used, in certainembodiments, one of the acidic copolymer and the basic copolymeradvantageously need only comprise up to about 5% by weight of the blend,typically about 0.5% by weight to about 5% by weight of the blend.

In another embodiment, the hot-melt adhesive composition comprises ablend of:

an acidic homopolymer; and

a basic copolymer derived from a group of monomers comprising at leastone basic monomer.

In certain variations of this embodiment, the group of monomerscomprises at least about 15% by weight of basic monomers; although,lower amounts may also be used. Advantageously, although more may beused, the acidic homopolymer need only comprise as little as up to about5% by weight of the blend, most typically about 0.5% by weight to about5% by weight of the blend, in order to achieve hot-melt adhesives havingcohesive strengths suitable for intended applications.

In yet another embodiment, the hot-melt adhesive composition comprises ablend of:

an acidic copolymer derived from monomers comprising at least onemonomer selected from the group consisting of an ethylenicallyunsaturated sulfonic acid, an ethylenically unsaturated phosphonic acid,and mixtures thereof and at least one non-acidic copolymerizablemonomer; and

a basic homopolymer.

In certain variations of this embodiment, the monomers, from which theacidic copolymer is derived, comprise at least about 15% by weight ofacidic monomers;

although, lower amounts may also be used. Advantageously, although moremay be used, the basic homopolymer need only comprise as little as up toabout 5% by weight of the blend in certain variations of thisembodiment, most typically about 0.5% by weight to about 5% by weight ofthe blend, in order to achieve hot-melt adhesives having cohesivestrengths suitable for intended applications.

Further embodiments of the invention include substrates and tapes (e.g.,single-sided and double-sided tapes) comprising the hot-melt adhesivecompositions. Also disclosed are methods for preparing and using thehot-melt adhesive compositions. For example, in one embodiment, a methodfor improving cohesive strength of a hot-melt adhesive comprises thesteps of:

providing a basic hot-melt adhesive (i.e., one that can be titrated withan acid); and

blending an acidic copolymer with the hot-melt adhesive,

wherein the acidic copolymer is derived from monomers comprising atleast about 15% by weight of acidic monomers. In another embodiment, amethod for improving cohesive strength of a hot-melt adhesive comprisesthe steps of:

providing an acidic hot-melt adhesive (i.e., one that can be titratedwith a base); and

blending a basic copolymer with the hot-melt adhesive,

wherein the basic copolymer is derived from monomers comprising at leastabout 15% by weight of basic monomers. The methods may also furthercomprise the step of applying the hot-melt adhesive to a substrate.

By utilizing polymeric blends of the present invention, hot-meltadhesives advantageously have one or more of the followingcharacteristics: increased cohesive strength, miscibility between thepolymers in the blends is promoted, variability in form (e.g., pelletform versus pumpable form) in which the polymers can be introduced intoa hot-melt adhesive, greater formulation latitude, a balance betweenpeel adhesion and cohesive strength, more efficient and uniformthermally reversible crosslinking, and cost-effectiveness.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hot-melt adhesives of the present invention are “thermally reversiblycrosslinked.” That is, the adhesives of the present invention remainhot-melt processable after application and cooling, yet retaincharacteristics of a crosslinked adhesive (e.g., solvent and/or creepresistance). Thus, the adhesives may be repeatedly hot-melt processed,while still providing adhesives with improved cohesive strength.

A primary advantage of the present blends is that they have improvedcohesive strength after application without the need for subsequentcuring steps. Additional curing steps may be utilized, however, if sodesired. Such additional curing steps include exposing the adhesive toradiation, such as ultraviolet or electron beam radiation.

Hot-melt adhesives of the present invention comprise a blend of at leastone acidic polymer and at least one basic polymer. Preferably, at leastone of the acidic polymer and the basic polymer is a hot-melt adhesive(i.e., having properties of a hot-melt adhesive). The followingdescription of such hot-melt adhesive blends and their use will makereference to terms which are hereinafter defined as follows:

“Pressure-sensitive adhesives (PSAs)” are well known to one of ordinaryskill in the art to possess properties including the following: (1)aggressive and permanent tack, (2) adherence with no more than fingerpressure, (3) sufficient ability to hold onto an adherend, and (4)sufficient cohesive strength to be removed cleanly from the adherend.PSAs are one example of a preferred hot-melt adhesive blend inaccordance with the present invention.

“Heat-activatable adhesive systems” are another preferred hot-meltadhesive blend in accordance with the present invention.Heat-activatable adhesives are substantially nontacky at roomtemperature, but become tacky upon heating. Heat-activatable systems,unlike PSA systems, rely on a combination of pressure and heat to bondto a surface.

“Acidic monomers” are those monomers that can be titrated with a base.

“Basic monomers” are those monomers that can be titrated with an acid.

“Polymer” refers to macromolecular materials having at least fiverepeating monomeric units, which may or may not be the same. The termpolymer, as used herein, encompasses homopolymers and copolymers.

An “acidic copolymer” is a polymer that is derived from at least oneacidic monomer and at least one non-acidic copolymerizable monomer(i.e., a monomer that can not be titrated with a base). In a preferredembodiment, at least one copolymerizable monomer is a (meth)acrylatemonomer (e.g., an alkyl (meth)acrylate monomer). The acidic copolymermay optionally be derived from other copolymerizable monomers, such asvinyl monomers and basic monomers, as long as the copolymer can still betitrated with a base. Thus, usually more acidic monomers are utilized toprepare the acidic copolymers than basic monomers. Preferably, however,in order to efficiently impart cohesive strength to the adhesive,essentially no basic monomers (i.e., the copolymerizable monomersinclude about 5 wt. % or less of basic monomers, but most preferably,the copolymerizable monomers are free of basic monomers) are utilized toprepare the acidic copolymers of the present invention.

A “basic copolymer” is a polymer that is derived from at least one basicmonomer and at least one non-basic copolymerizable monomer (i.e., amonomer that can not be titrated with an acid). In a preferredembodiment, at least one copolymerizable monomer is a (meth)acrylatemonomer (e.g., an alkyl (meth)acrylate monomer). The basic copolymer mayoptionally be derived from other copolymerizable monomers, such as vinylmonomers and acidic monomers, as long as the copolymer can still betitrated with an acid. Thus, it is preferred that more basic monomersare utilized to prepare the basic copolymers than are acidic monomers.Most preferably, however, in order to efficiently impart cohesivestrength to the adhesive, essentially no acidic monomers (i.e., thecopolymerizable monomers include about 5 wt. % or less of acidicmonomers, but most preferably, the copolymerizable monomers are free ofacidic monomers) are utilized to prepare basic copolymers of the presentinvention.

An “acidic homopolymer” is a polymer that is derived solely from acidicmonomers. The acidic monomers may be the same or different, so long asthey are copolymerizable. Preferably, all of the acidic monomers are thesame.

A “basic homopolymer” is a polymer that is derived solely from basicmonomers. The basic monomers may be the same or different, so long asthey are copolymerizable. Preferably, all of the basic monomers are thesame.

Acidic Monomers

Useful acidic monomers include, but are not limited to, those selectedfrom ethylenically unsaturated carboxylic acids, ethylenicallyunsaturated sulfonic acids, ethylenically unsaturated phosphonic acids,and mixtures thereof. Examples of such compounds include those selectedfrom acrylic acid, methacrylic acid, itaconic acid, fumaric acid,crotonic acid, citraconic acid, maleic acid, oleic acid, β-carboxyethylacrylate, 2-sulfoethyl methacrylate, styrene sulfonic acid,2-acrylamido-2-methylpropane sulfonic acid, vinyl phosphonic acid, andthe like, and mixtures thereof Due to their availability, particularlypreferred acidic monomers are the ethylenically unsaturated carboxylicacids. When even stronger acids are desired, particularly preferredacidic monomers include the ethylenically unsaturated sulfonic acids andethylenically unsaturated phosphonic acids. Sulfonic and phosphonicacids generally provide a stronger interaction with the basic polymer.This stronger interaction can lead to greater improvements in cohesivestrength, as well as higher temperature resistance and solventresistance of the hot-melt adhesive.

When the acidic polymer is a copolymer, the ratio of acidic monomers tonon-acidic copolymerizable monomers utilized varies depending on desiredproperties of the resulting hot-melt adhesive. The properties of thehot-melt adhesive can also be adjusted by varying the amount of theacidic copolymer in the blend.

Generally, as the proportion of acidic monomers used in preparing theacidic copolymer increases, cohesive strength of the resulting adhesiveincreases. The proportion of acidic monomers is usually adjusteddepending on the proportion of acidic copolymer present in the blends ofthe present invention. Preferably, the proportion of acidic monomers isless than about 15% by weight when the acidic copolymer is a pressuresensitive hot-melt adhesive. In other embodiments, the proportion ofacidic monomers is preferably greater than about 15% by weight,especially when the basic polymer is a copolymer derived from less thanabout 15% by weight of basic monomers. More preferably, in suchembodiments, the proportion of acidic monomers is at least about 25% byweight. Even more preferably, in such embodiments, the proportion ofacidic monomers is at least about 35% by weight. In certain embodiments,preferably, the proportion of acidic monomers is at least about 50% byweight. More preferably, for certain embodiments, the proportion ofacidic monomers is at least about 60% by weight.

Basic Monomers

A wide variety of basic monomers are useful in the present invention.Preferably, the basic monomer is a non-nucleophilic (i.e., having nohydrogen atoms directly bonded to nitrogen atoms) amine-functionalmonomer. A preferred basic copolymerizable monomer is represented byFormula (II).

wherein a is 0 or 1; R is selected from H— and CH₃—, X is selected from—O— and —NH—; and Y is a divalent linking group, preferably comprisingabout 1 to about 5 carbon atoms for ease of availability. Examples ofspecific Y groups include those selected from the groups consisting of—(CH₂)_(n)—, wherein n represents an integer of 1 to 5, and divalentalkyl groups having internal linkages selected from ether linkinggroups, thioether linking groups, keto linking groups, urea linkinggroups, urethane linking groups, amido linking groups, combinationsthereof, and the like.

Am is a tertiary amine fragment, such as the group:

wherein R¹ and R² are independently selected from an alkyl group, anaryl group, a cycloalkyl group, and an arenyl group. R¹ and R² in theabove group may also form a heterocycle. Am can, alternatively, comprisea monovalent aromatic radical comprising 1 to 3 aromatic ringstructures, preferably 1, wherein at least 1 aromatic ring structurecontains a basic nitrogen atom as a member of the ring structure itself,such as pyridinyl and substituted pyridinyl. Am can also comprise otherbasic heterocycles, such as imidazole or substituted imidazole. In allembodiments, Y, R¹, and R² may also comprise heteroatoms, such as O, S,N, etc.

The basicity of the monomers utilized in the present invention isdefined by their substitution. R¹ and/or R² may in certain situationsrepresent an electron-donating group. Such substituents that increasethe electron density on a nitrogen by field effects (or resonance in thecase of aromatic bases such as pyridine) will increase the basicity ofthe nitrogen. Alkyl groups are preferred for inclusion in R¹ and R² dueto their electron-donating nature. Examples of electron-donating groupsthat R¹ and/or R² can comprise include, but are not limited to, thoseselected from —C(R³)₃, —CH(³)₂, —CH₂(R³), and —CH₃, wherein R³represents an alkyl group, typically an alkyl group comprising about 1carbon atom to about 6 carbon atoms. Most preferably, R¹ and R² arelinear, alkyl groups. The higher the degree of substitution on thenitrogen by such alkyl groups, the higher the basicity of the monomer.

Conversely, substituents which decrease the electron density on thenitrogen of a basic copolymerizable monomer, such as a phenyl group,will reduce the basicity of the monomer. Preferably, R1 and R² do notcontain electron-withdrawing atoms (e.g., halogens, —COOH, —NO₂, etc.)directly connected to the nitrogen within the amine-functional monomer.However, electron-withdrawing atoms separated from the nitrogen atom by,for example, an alkane structure, are suitable for inclusion in thegroup Am.

A wide variety of basic monomers of Formula II can be utilized for suchcopolymers. For example, N,N-dimethylaminopropyl methacrylamide(DMAPMAm); N,N-diethylaminopropyl methacrylamide (DEAPMAm);N,N-dimethylaminoethyl acrylate (DMAEA); N,N-diethylaminoethyl acrylate(DEAEA); N,N-dimethylaminopropyl acrylate (DMAPA);N,N-diethylaminopropyl acrylate (DEAPA); N,N-dimethylaminoethylmethacrylate (DMAEMA); N,N-diethylaminoethyl methacrylate (DEAEMA);N,N-dimethylaminoethyl acrylamide (DMAEAm); N,N-dimethylaminoethylmethacrylamide (DMAEMAm); N,N-diethylaminoethyl acrylamide (DEAEAm);N,N-diethylaminoethyl methacrylamide (DEAEMAm); N,N-dimethylaminoethylvinyl ether (DMAEVE); N,N-diethylaminoethyl vinyl ether (DEAEVE); andmixtures thereof are useful basic monomers. Other basic monomers thatcan be used include 4-(N,N-dimethylamino)-styrene (DMAS);4-(N,N-diethylamino)-styrene (DEAS); vinylpyridine; vinylimidazole; andmixtures thereof Many of these monomers are commercially available fromRohm Tech, Inc., of Maiden, Mass.; CPS Chemical Co., Inc., of OldBridge, N.J.; Rohm & Haas, of Philadelphia, Pa.; and/or Aldrich ChemicalCo., Inc., of Milwaukee, Wis.

When the basic polymer is a copolymer, the ratio of basic monomers tonon-basic copolymerizable monomers utilized varies depending on desiredproperties of the resulting hot-melt adhesive. The properties of thehot-melt adhesive can also be adjusted by varying the amount of thebasic copolymer in the blend.

Generally, as the proportion of basic monomers used in preparing thebasic copolymer increases, cohesive strength of the resulting adhesiveincreases. The proportion of basic monomers is usually adjusteddepending on the proportion of basic copolymer present in the blends ofthe present invention. Preferably, the proportion of basic monomers isless than about 15% by weight when the basic copolymer is a pressuresensitive hot-melt adhesive. In other embodiments, the proportion ofbasic monomers is preferably greater than about 15% by weight,especially when the acidic polymer is a copolymer derived from less thanabout 15% by weight of acidic monomers. In such embodiments, morepreferably, the proportion of basic monomers is at least about 25% byweight. Even more preferably, the proportion of basic monomers is atleast about 35% by weight. In certain embodiments, preferably, theproportion of basic monomers is at least about 50% by weight. Morepreferably, for certain embodiments, the proportion of basic monomers isat least about 60% by weight.

Optional Vinyl Monomers

When used, vinyl monomers useful in the acidic and basic copolymersinclude N-vinyl pyrrolidone, N-vinyl caprolactam, acrylonitrile, N-vinylformamide, vinyl esters (e.g., vinyl acetate), (meth)acrylamide,styrene, substituted styrene (e.g., α-methyl styrene), vinyl toluene,vinyl chloride, vinyl propionate, and mixtures thereof.

When the acidic polymer and/or the basic polymer is a copolymer, it ispreferred that at least one of the copolymers is a (meth)acrylatecopolymer. Most preferably, each of the copolymers is a (meth)acrylatecopolymer. Accordingly, each (meth)acrylate copolymer is preferablyderived from at least one (meth)acrylate monomer.

(Meth)acrylate Monomers

(Meth)acrylate copolymers useful in the invention contain at least onemonofunctional unsaturated monomer selected from the group consisting of(meth)acrylate esters of non-tertiary alkyl alcohols, the alkyl groupsof which comprise from about 1 to about 20, preferably about 1 to about18 carbon atoms; and mixtures thereof. Preferred (meth)acrylate monomershave the following general Formula (I):

wherein R¹ is H or CH₃, the latter corresponding to where the(meth)acrylate monomer is a methacrylate monomer. R² is broadly selectedfrom linear, branched, aromatic, or cyclic hydrocarbon groups.Preferably, R² is a linear or branched hydrocarbon group. The number ofcarbon atoms in the hydrocarbon group is preferably about 1 to about 20,and more preferably about 1 to about 18. When R² is a hydrocarbon group,it can also include heteroatoms (e.g., oxygen or sulfur).

Criteria to consider when selecting R² include cost and the form inwhich the copolymer will be incorporated into the hot-melt adhesive. Themanner of blending the components of the hot-melt adhesive varies. Forexample, each component can be incorporated into the hot-melt adhesivein a wide variety of forms, such as a pumpable form or a pelleted form.When incorporating a pumpable form of a copolymer into the hot-meltadhesive, a wide variety of (meth)acrylate copolymers can be used.

When incorporating a pelleted form of a copolymer into the hot-meltadhesive, the glass transition temperature (Tg) of the (meth)acrylatecopolymer is controlled, preferably such that the copolymer is not tackyand free of blocking (i.e., such that pellets do not stick together,especially when under pressure). Thus, copolymers having a Tg of atleast room temperature (i.e., 22° C. to 25° C.) and more preferably a Tgof greater than about 50° C. are preferred. R² is, thus, selectedaccordingly. Alternatively, monomers having a crystalline melting point(Tm) can be used to make pelleted copolymers. When used in proportionssuch that the resulting copolymer has a Tm of greater than the storagetemperature, storage-stable pellets can be obtained. For ease ofstorage, preferably such pelleted copolymers have a Tm of at least about50° C. However, the Tm should be below the desired melt processingtemperature to facilitate incorporating the pellets into a blend.

Examples of suitable (meth)acrylate monomers useful in the presentinvention include, but are not limited to, benzyl methacrylate, n-butylacrylate, n-butyl methacrylate, cyclohexyl acrylate, cyclohexylmethacrylate, decyl acrylate, 2-ethoxy ethyl acrylate, 2-ethoxy ethylmethacrylate, ethyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate,n-hexadecyl acrylate, n-hexadecyl methacrylate, hexyl acrylate, isoamylacrylate, isobomyl acrylate, isobornyl methacrylate, isobutyl acrylate,isodecyl acrylate, isodecyl methacrylate, isononyl acrylate, isooctylacrylate, isooctyl methacrylate, isotridecyl acrylate, lauryl acrylate,lauryl methacrylate, 2-methoxy ethyl acrylate, methyl acrylate, methylmethacrylate, 2-methyl butyl acrylate, 4-methyl-2-pentyl acrylate,1-methylcyclohexyl metbacrylate, 2-methylcyclohexyl methacrylate,3-methylcyclohexyl methacrylate, 4-methylcyclohexyl methacrylate,octadecyl acrylate, octadecyl methacrylate, n-octyl acrylate, n-octylmethacrylate, 2-phenoxy ethyl methacrylate, propyl acrylate,n-tetradecyl acrylate, n-tetradecyl methacrylate, and mixtures thereofParticularly preferred are the alkyl (meth)acrylate monomers.

The amounts and types of monomers used in preparing the acidic and basiccopolymers of the present invention can be varied to provide a range ofadhesive properties desired for the end use. Higher crosslinking densityand cohesive strength can be obtained by increasing amounts ofcopolymerizable basic or acidic monomer utilized in preparing copolymersof the present invention, while lowering the amounts of thecopolymerizable basic or acidic monomer can reduce the crosslinkingdensity within the blend. If one or both of the acidic polymer and thebasic polymer are copolymers, then it is preferred that at least one ofthe copolymers is derived from monomers comprising greater than about15% by weight of acidic or basic monomers, respectively, so as toprovide sufficiently improved cohesive strength. More preferably, atleast one of the copolymers is derived from monomers comprising at leastabout 25% by weight; even more preferably, at least about 35% by weight;yet even more preferably, at least about 50% by weight; and mostpreferably, at least about 60% by weight of acidic or basic monomers,respectively.

If one of the acidic or basic polymer requires pressure-sensitiveadhesive characteristics, then a corresponding copolymer can be tailoredto have a resultant glass transition temperature (Tg) of less than about0° C. Particularly preferred pressure-sensitive adhesive copolymers are(meth)acrylate copolymers. Such copolymers typically are derived frommonomers comprising about 40% by weight to about 98% by weight,preferably at least 70% by weight, more preferably at least 85% byweight, most preferably about 90% by weight, of at least one alkyl(meth)acrylate monomer that, as a homopolymer, has a Tg of less thanabout 0° C. Basic (meth)acrylate copolymers typically are derived frommonomers comprising about 2% by weight to about 60% by weight,preferably about 10% by weight to about 40% by weight, of acopolymerizable basic monomer. Acidic (meth)acrylate copolymerstypically are derived from monomers comprising about 2% by weight toabout 30% by weight, preferably about 2% by weight to about 15% byweight, of a copolymerizable acidic monomer. Examples of such alkyl(meth)acrylate monomers are those in which the alkyl groups comprisefrom about 4 carbon atoms to about 12 carbon atoms and include, but arenot limited to, n-butyl acrylate, 2-ethylhexyl acrylate, isooctylacrylate, isononyl acrylate, isodecyl acrylate, and mixtures thereofOptionally, other vinyl monomers and alkyl (meth)acrylate monomerswhich, as homopolymers, have a Tg greater than 0C., such as methylacrylate, methyl methacrylate, ethyl acrylate, isobornyl acrylate, vinylacetate, styrene, and the like, may be utilized in conjunction with oneor more if the alkyl (meth)acrylate monomers and copolymerizable basicor acidic monomers, provided that the Tg of the resultant (meth)acrylatecopolymer is less than about 0° C.

Heat-activatable adhesives can be obtained by preparing copolymers fromthe same components used to form the pressure-sensitive adhesivecopolymers discussed above. Preferably, the heat-activatable adhesivesare prepared from (meth)acrylate monomers. The low Tg alkyl(meth)acrylate monomers (i.e., those that, as a homopolymer, have a Tgof less than about 0° C.), copolymerizable basic or acidic monomers,optional vinyl monomers, and high Tg alkyl (meth)acrylate monomers(i.e., those that as a homopolymer, have a Tg of greater than about 0°C.) are used in different proportions, however, such that the final(meth)acrylate copolymer has a Tg of about 25° C. to about 30° C. belowthe desired heat-activation temperature. To increase the copolymer Tg,higher levels of the basic monomer, acidic monomer, and/or higher levelsof the high Tg alkyl (meth)acrylate monomer can be used. The proportionof the high Tg monomers is dictated by the final Tg requirement.

Cohesive strength of the resulting hot-melt adhesive blends ispreferably at least greater than the cohesive strength of the individualpolymeric components (e.g., the hot-melt adhesive). The final cohesivestrength depends, however, on the amount and type of each polymerpresent in the hot-melt adhesive, as well as other components (e.g.,tackifiers, plasticizers, etc.) of the hot-melt adhesive system. Theshear strength of an adhesive is related to its cohesive strength. Animprovement in shear strength of hot-melt adhesives is one advantage ofutilizing the present blends.

Advantageously, increased cohesive strength can be achieved without anadditional curing step. However, other types of curing (i.e., thermal,ultraviolet or electron beam radiation) can also be used in conjunctionwith the present hot-melt adhesive blends. Generally, however, they arenot necessary.

Other advantages of utilizing blends of the present invention includethe ability to provide thick adhesive coatings with sufficientcrosslinking throughout the thickness. Previously, this was oftendifficult and problematic when utilizing photoactivated crosslinkingagents because it was difficult for UV-radiation to penetrate the entirethickness of certain adhesive coatings.

In the most preferred embodiment, the hot-melt adhesive blend comprisesat least one acidic (meth)acrylate copolymer and at least one basic(meth)acrylate copolymer. By utilizing (meth)acrylate copolymer blendsfor the hot-melt adhesives, many advantages are obtained. Althoughblends of at least two copolymers are preferred, however, some of theseadvantages can also be obtained when only one of the polymers is acopolymer.

For example, miscibility between the two copolymers is promoted becauseboth copolymers are (meth)acrylate copolymers. Miscibility is reflectedby the coatibility of the hot-melt adhesive blend (i.e., the adhesivescan be readily coated using conventional techniques without significantdetrimental defects, such as streaks, particles, or a grainy texture,etc.). As used herein, miscibility does not mean that optically clearblends have to be obtained or that the components are miscible on amolecular scale. Advantageously, miscibility can be achieved atrelatively lower temperatures, enabling the hot-melt adhesives to bepotentially applied to a substrate at lower temperatures. Due to theincreased miscibility of the adhesive components, organic solvents orwater are not required when blending or coating the hot-melt adhesivesystem. Thus, the present blends are particularly well suited for use inhot-melt adhesive systems—systems that are essentially 100% solidssystems. Preferably, such systems have no more than about 5% organicsolvents or water, more preferably no more than about 3% organicsolvents or water. Most preferably, such systems are free of organicsolvents and water.

Also, the use of copolymers allows for variability in form (e.g., pelletform versus pumpable form) in which the polymers can be introduced intothe hot-melt adhesive. This is advantageous because it allows forvariability to meet operator needs (e.g., compatibility with a widevariety of equipment).

Another advantage that blends, especially copolymers blends, provide isgreater formulation latitude. That is, changes in the degree ofcrosslinking can be effectuated, for example, by varying the ratio ofindividual components in the blends. By utilizing copolymers, theproportion of the acidic and basic monomers is diluted by the presenceof the copolymerizable monomers (e.g., (meth)acrylate monomers). Thus,small changes in crosslinking density can be accomplished without asmuch precision in measurement, allowing for more formulation latitude.It should also be noted that oftentimes equipment utilized in suchprocesses is not available for measuring components to an acceptabledegree of accuracy, as required when utilizing, for example,homopolymers or low molecular weight crosslinking additives in theblends.

Changes in the degree of crosslinking can also be effectuated bytailoring the distance between crosslinks in an adhesive. For example,by varying the proportion of acidic and basic monomers used in preparingthe copolymers, the degree of crosslinking can be affected. In thismanner, a balance between peel adhesion and cohesive strength can bereadily achieved in the hot-melt adhesive.

Yet another advantage of utilizing copolymer blends is that moreefficient and uniform crosslinking can occur, as compared to, forexample, when one copolymer is blended with a homopolymer. Theseattributes are believed to be a result of the blending capabilities ofthe copolymers. Homopolymers do not blend as well because acid/baseinteractions at the point of addition are stronger due to the higherproportion (i.e., 100%) of acidic or basic monomers in the homopolymer.This strong interaction often prevents the homopolymer from diffusingefficiently and uniformly through the hot-melt adhesive. In contrast,the proportion of acidic/basic monomers in the copolymers is diluted dueto the copolymerization of other monomers (e.g., (meth)acrylatemonomers) therewith. This moderates such strong acid/base interactionsat the point of addition, thus, facilitating mixing of the polymericcomponents.

Finally, cost effectiveness is another advantage of utilizing copolymersin the blends. For example, less expensive (meth)acrylate monomers canbe utilized in one of the copolymers. In that way, less expensive(meth)acrylate monomers can act as an “extender” for more expensive(meth)acrylate monomers contained in the other copolymer. Similarly, the(meth)acrylate monomers can act as an “extender” for more expensivebasic or acidic monomers. Furthermore, the added cost of ultraviolet orelectron beam radiation equipment is not necessary when utilizing thepresent hot-melt blends because such post-polymerization processing isnot necessary to achieve desired cohesive strengths.

Polymerization Methods

The polymers herein can be prepared by any conventional free radicalpolymerization method, including solution, radiation, bulk, dispersion,emulsion, and suspension processes.

In one solution polymerization method, the monomers, along with asuitable inert organic solvent, are charged into a four-neck reactionvessel that is equipped with a stirrer, a thermometer, a condenser, anaddition funnel, and a thermowatch. A concentrated thermal free radicalinitiator solution is added to the addition funnel. The whole reactionvessel, addition funnel, and their contents are then purged withnitrogen to create an inert atmosphere. Once purged, the solution withinthe vessel is heated to an appropriate temperature to activate the freeradical initiator to be added, the initiator is added, and the mixtureis stirred during the course of the reaction. A 98% to 99% conversionshould be obtained in about 20 hours.

Another polymerization method is ultraviolet (UV) radiation-initiatedphotopolymerization of the monomer mixture. After pre-polymerization toa coatable viscosity, the mixture, along with a suitable photoinitiator,is coated onto a flexible carrier web and polymerized in a sufficientlyinert (i.e., essentially oxygen free) atmosphere (e.g., a nitrogenatmosphere). A sufficiently inert atmosphere can be achieved by coveringa layer of the photoactive coating with a plastic film that issubstantially transparent to ultraviolet radiation and irradiatingthrough the plastic film in air using low intensity, fluorescent-typeultraviolet lamps that generally give a total radiation dose of about500 milliJoules/cm².

Bulk polymerization methods, such as the continuous free radicalpolymerization method described by Kotnour et al. in U.S. Pat. Nos.4,619,979 and 4,843,134; the essentially adiabatic polymerizationmethods using a batch reactor described by Ellis in U.S. Pat. No.5,637,646; suspension polymerization processes described by Young et al.in U.S. Pat. No. 4,833,179; and, the methods described for polymerizingpackaged pre-adhesive compositions described by Hamer et al. in PCTPublication No. WO 97/33945 may also be utilized to prepare thepolymers.

Suitable thermal free radical initiators which may be utilized include,but are not limited to, those selected from azo compounds, such as2,2′-azobis(isobutyronitrile); hydroperoxides, such as tert-butylhydroperoxide; and, peroxides, such as benzoyl peroxide andcyclohexanone peroxide. Photoinitiators which are useful according tothe invention include, but are not limited to, those selected frombenzoin ethers, such as benzoin methyl ether or benzoin isopropyl ether;substituted benzoin ethers, such as anisole methyl ether; substitutedacetophenones, such as 2,2-diethoxyacetophenone and2,2-dimethoxy-2-phenyl acetophenone; substituted alpha-ketols, such as2-methyl-2-hydroxy propiophenone; aromatic sulfonyl chlorides, such as2-naphthalene sulfonyl chloride; and, photoactive oximes, such as1-phenyl-1,2-propanedione-2-(ethoxycarbonyl)oxime. For both thermal- andradiation-induced polymerizations, the initiator is present in an amountof about 0.05 percent to about 5.0 percent by weight based upon thetotal weight of the monomers.

Preferably, the polymers are polymerized without solvent. Yet, suitableinert organic solvent, if desired, may be any organic liquid which issufficiently inert to the reactants and product such that it will nototherwise adversely affect the reaction. Such solvents include ethylacetate, acetone, methyl ethyl ketones, and mixtures thereof If used,the amount of solvent is generally about 30-80% by weight based on thetotal weight of the reactants (monomer and initiator) and solvent. Insuch cases, the solvent is generally removed from the polymers prior toblending.

Chain transfer agents can also be utilized when polymerizing thepolymers described herein to control the molecular weight of thepolymers. Suitable chain transfer agents include halogenatedhydrocarbons (e.g., carbon tetrabromide) and sulfur compounds (e.g.,lauryl mercaptan, butyl mercaptan, ethanethiol, and 2-mercaptoether).

The amount of chain transfer agent that is useful depends upon thedesired molecular weight and the type of chain transfer agent. Organicsolvents (e.g., toluene, isopropanol, and ethyl acetate) can also beused as chain transfer agents, but they generally are not as active as,for example, sulfur compounds. The chain transfer agent is typicallyused in amounts from about 0.001 parts to about 10 parts; preferably,0.01 to about 0.5 parts; and most preferably from about 0.02 parts toabout 0.20 parts based on total weight of the monomers.

Blending

Blending of the polymers is done by any method that results in asubstantially homogenous distribution of the acidic polymer and thebasic polymer. The polymers can be blended using several methods. Forexample, the polymers can be blended in-situ by sequentialpolymerization. Alternatively, the polymers can be blended by meltblending, solvent blending, or any suitable physical means.

For example, the polymers can be melt blended by a method as describedby Guerin et al. in U.S. Pat. No. 4,152,189. That is, all solvent (ifused) is removed from each polymer by heating to a temperature of about150° C. to about 175° C. at a pressure of about 5 Torr to about 10 Torr.Then, the polymers are weighed into a vessel in the desired proportions.The blend is then formed by heating the contents of the vessel to about175° C., while stirring.

Although melt blending is preferred, the adhesive blends of the presentinvention can also be processed using solvent blending. The acidic andbasic polymers should be substantially soluble in the solvents used.

Physical blending devices that provide dispersive mixing, distributivemixing, or a combination of dispersive and distributive mixing areuseful in preparing homogenous blends. Both batch and continuous methodsof physical blending can is be used. Examples of batch methods includeBRABENDER (using a BRABENDER PREP CENTER, available from C.W. BrabenderInstruments, Inc.; South Hackensack, N.J.) or BANBURY internal mixingand roll milling (using equipment available from FARREL COMPANY;Ansonia, Conn.). Examples of continuous methods include single screwextruding, twin screw extruding, disk extruding, reciprocating singlescrew extruding, and pin barrel single screw extruding. The continuousmethods can include utilizing both distributive elements, such as cavitytransfer elements (e.g., CTM, available from RAPRA Technology, Ltd.;Shrewsbury, England) and pin mixing elements, static mixing elements anddispersive elements (e.g., MADDOCK mixing elements or SAXTON mixingelements as described in “Mixing in Single-Screw Extruders,” Mixing inPolymer Processing, edited by Chris Rauwendaal (Marcel Dekker Inc.: NewYork (1991), pp. 129, 176-177, and 185-186).

Due to the sometimes strong acid/base interaction between the acidicpolymer and basic polymer of the adhesive blend, homogenous distributionof the polymers may be difficult. Thus, to assist in blending, it may bepreferable to add a neutralizing agent to temporarily neutralize acidicfunctional groups of the acidic polymer, basic functional groups of thebasic polymer, or both. After blending, the neutralizing agent can beevaporated, regenerating acid/base interactions between the polymers.Examples of neutralizing agents for basic functional groups includevolatile organic acids, such as formic acid and acetic acid. Usefulneutralizing agents for acidic functional groups include volatileorganic bases, such as ammonia, trimethyl amine, and triethylamine.

Preferably, one of the polymers has adhesive properties (e.g.,pressure-sensitive adhesive or heat-activated adhesive properties) andconstitutes a major proportion of the blend. The other polymer thenconstitutes a minor proportion of the blend and is adjusted to achievedesired properties of the resulting adhesive. Although, more may beused, only small amounts of the minor component are needed foreffectiveness in certain embodiments. Preferably about 0.5% by weight toabout 15% by weight more preferably about 1% by weight to about 10% byweight, and most preferably about 1% by weight to about 5% by weight ofthe minor component based on total weight of the polymeric components isused in the blend.

Other Additives

Other additives may also be blended into the hot-melt adhesive prior toapplication thereof, depending on the desired properties of the appliedadhesive. For example, if a pressure-sensitive hot-melt adhesive isdesired, tackifiers can be added if the crosslinking density causes asubstantial decrease in the amount of tack below that which is desired.Plasticizers can also be added.

Photoinitiators and photocrosslinkers can be added for optionalsubsequent curing by UV-irradiation. Although not present in thepreferred embodiments, conventional crosslinking agents (both physicaland chemical crosslinking agents) can also be utilized in allembodiments of the present blends.

Application of the Hot-Melt Adhesive

The hot-melt adhesive is readily applied to a substrate. For example,the hot-melt adhesive can be applied to sheeting products (e.g.,decorative, reflective, and graphical), labelstock, and tape backings.The substrate can be any suitable type of material depending on thedesired application. Typically, the substrate comprises a nonwoven,paper, polypropylene (e.g., biaxially oriented polypropylene (BOPP)),polyethylene, polyester (e.g., polyethylene terephthalate), or releaseliner (e.g., siliconized liner).

Thus, hot-melt adhesives according to the present invention can beutilized to form tape, for example. To form a tape, the hot-meltadhesive is coated onto at least a portion of a suitable backing. Arelease material (e.g., low adhesion backsize) can be applied to theopposite side of the backing, if desired. When double-sided tapes areformed, the hot-melt adhesive is coated onto at least a portion of bothsides of the backing.

Hot-melt adhesives can be applied to a substrate using methods wellknown to one of ordinary skill in the art. The acidic polymer and basicpolymer can be blended and applied using melt extrusion techniques toform the hot-melt, thermally reversible crosslinked adhesive blend ofthe present invention.

The adhesive blend can be formed into an adhesive film or coating byeither continuous or batch processes. An example of a batch process isthe placement of a portion of the blend between a substrate to which thefilm or coating is to be adhered and a surface capable of releasing theadhesive film or coating to form a composite structure. The compositestructure can then be compressed at a sufficient temperature andpressure to form an adhesive coating or layer of a desired thicknessafter cooling. Alternatively, the adhesive blend can be compressedbetween two release surfaces and cooled to form a heat-activatableadhesive film or a pressure-sensitive adhesive transfer tape useful inlaminating applications.

Continuous forming methods include drawing the hot-melt adhesive systemout of a film die and subsequently contacting the drawn adhesive blendto a moving plastic web or other suitable substrate. A relatedcontinuous method involves extruding the adhesive blend and a coextrudedbacking material from a film die and cooling the layered product to forman adhesive tape. Other continuous forming methods involve directlycontacting the adhesive blend to a,rapidly moving plastic web or othersuitable preformed substrate. Using this method, the adhesive blend isapplied to the moving preformed web using a die having flexible dielips, such as a rotary rod die. After forming by any of these continuousmethods, the adhesive films or layers can be solidified by quenchingusing both direct methods (e.g., chill rolls or water baths) andindirect methods (e.g., air or gas impingement).

Although coating out of solvent is not preferred, blends can be coatedusing a solvent-based method. For example, the blend can be coated bysuch methods as knife coating, roll coating, gravure coating, rodcoating, curtain coating, and air knife coating. The coatedsolvent-based adhesive blend is then dried to remove the solvent and, ifused, neutralizing agent. Preferably, the coated solvent-based adhesiveblend is subjected to increased temperatures, such as those supplied byan oven, to expedite drying of the adhesive.

The cohesive strength of the resulting hot-melt adhesive develops uponcooling to ambient temperature after application. To further enhancecohesive strength of the adhesive, it may be useful to maintain theadhesive at elevated application temperatures for longer periods of timeprior to cooling thereof. One way this can be accomplished is by heatingthe substrate on which the adhesive is coated.

The blends and polymers herein are exemplified in the followingexamples. These examples are merely for illustrative purposes only andare not meant to be limiting on the scope of the appended claims. Thefollowing data may, at times, show variability in results. This can beexpected due to the various processing techniques utilized for preparingthe samples. What is noteworthy, however, is the increased shearstrength of the present hot-melt adhesives as compared to conventional,non-crosslinked hot-melt adhesives. All parts, percentages, ratios, etc.in the examples and the rest of the specification are by weight unlessindicated otherwise.

TEST METHODS

Prior to testing, all samples were conditioned for about 24 hours in aconstant temperature (23° C.), constant humidity (50% relative humidity)environment. Both the peel adhesion test and the shear strength testwere performed under the same atmospheric conditions.

Peel Adhesion

Peel adhesion is the force required to remove an adhesive-coated,flexible sheet material from a test panel. Peel adhesion is measured ata specific angle and rate of removal. In the following examples, thispeel adhesion force is expressed in Newtons/decimeter width (N/dm) ofthe coated sheet. Peel adhesion forces measured throughout are initialpeel adhesion forces taken at about one minute dwell time, unlessindicated to the contrary. These initial peel adhesion forces may not beindicative of aged peel adhesion forces that can be obtained.

The procedure followed was:

A strip (1.27 centimeter wide) of the adhesive-coated sheet was appliedto the horizontal surface of a clean glass test plate with at least 12.7lineal centimeter of both surfaces being in firm contact. One pass witha 2-kilogram hard rubber roller was used to apply the strip. The freeend of the coated strip was doubled back nearly touching itself so theangle of removal was 180°. The free end was attached to the adhesiontester scale, The glass test plate was clamped in the jaws of a tensiletesting machine that was capable of moving the plate away from the scaleat a constant rate of 2.3 meters/minute. The scale reading was recordedin Newtons as the tape was peeled from the glass surface. The data wasreported as the average of the range of numbers observed during thetest.

Shear Strength

Shear strength is a measure of the cohesiveness, or internal strength,of an adhesive. Shear strength is based upon the amount of forcerequired to pull an adhesive strip (tape) from a standard flat surfacein a direction parallel to the surface to which it has been affixed witha definite pressure. Shear strength was measured as the time, inminutes, required to pull a standard area of adhesive-coated sheetmaterial from a stailess steel test panel under the stress of aconstant, standard load. This test followed the procedure described inASTM D 3645M-88: “Holding Power of Pressure-sensitive Adhesive Tapes.”

The tests were conducted at room temperature (about 22° C. to about 25°C.) on strips of adhesive-coated sheet material applied to a stainlesssteel panel. A 0.127 decimeter square portion of each strip was in firmcontact with the panel and one end portion of the tape was free. Thepanel, with the adhesive-coated strip attached, was held in a rack suchthat the panel formed an angle of 178° with the extended free end of theadhesive-coated strip. The free end was tensioned by applying a force of1,000 grams to the free end of the adhesive-coated strip. An angle of 2°less than 180° was used in order to negate any peel forces. Thus, onlyshear forces were measured. The elapsed time for each adhesive-coatedstrip to separate from the test panel was recorded as the shearstrength. The test was discontinued after 10,000 minutes. The reportedresults are average values from testing two samples.

ABBREVIATIONS

AA acrylic acid BA n-butyl acrylate DMAEMA N,N-dimethylaminoethylmethacrylate ECR-180 a hydrogenated, synthetic hydrocarbon tackifier(commercially available from Exxon Co.; Houston, TX) ESACURE2,2-dimethoxy-1,2-diphenyl-1-ethanone photoinitiator KB-1 (commerciallyavailable from Sartomer Co.; Exton, PA) IOA isooctyl acrylate IRGANOXpentaerythritol tetrakis(3,5-di-tert-butyl-4- 1010hydroxyhydrocinnamate) antioxidant (commercially available from CibaGeigy Corp.; Hawthorne, NY) MMA methyl methacrylate ODA octadecylacrylate SANTICIZER a butyl benzylphthalate plasticizer 160(commercially available from the Monsanto Co.; St. Louis, MO) SEA2-sulfoethyl acrylate VAZO 52 2,2′-azo-bis(2,4-dimethylpentanenitrile)initiator (commercially available from E.I. duPont de Nemours & Co.;Wilmington, DE) VAZO 64 azo-bis(isobutyronitrile) initiator(commercially available from E.I. duPont de Nemours & Co.; Wilmington,DE) VAZO 67 2,2′-azo-bis(2-methylbutyronitrile) initiator (commerciallyavailable from E.I. duPont de Nemours & Co.; Wilmington, DE) VAZO 881,1-azo-bis(cyclohexanenitrile) initiator (commercially available fromE.I. duPont de Nemours & Co.; Wilmington, DE)

ACIDIC POLYMERS

Acidic Copolymer A (90/10 IOA/AA by wt. %)—In a 100-milliliter glassbottle, 21.6 grams IOA, 2.4 grams AA, 0.028 gram carbon tetrabromidechain transfer agent, and 36 grams ethyl acetate were mixed. To thismixture, 0.072 gram VAZO 64 was added. The bottle was then made inertwith nitrogen gas and sealed. The sealed bottle was tumbled in a 55° C.water bath for 24 hours. The resultant polymer had an inherent viscosity(IV) of 0.70 deciliter/gram (as measured in ethyl acetate at 25° C. at apolymer concentration of 0.2 gram/deciliter) and was coated on asiliconized polyester release liner. The coated solution was oven driedfor 15 minutes at 65° C. to recover the dried polymer.

Acidic Copolymer B—(90/10 IOA/AA by wt. %) A 90/10 IOA/AA acidicacrylate copolymer was prepared as described by Hamer et al. in Examples35 and 36 of PCT Publication No. WO 97/33945. A partially polymerizedpre-adhesive composition was prepared by mixing 90 parts IOA, 10 partsAA, 0.15 parts per hundred (pph) ESACURE KB-1 photoinitiator, and 0.025pph carbon tetrabromide chain transfer agent. The mixture was placed ina container and stirred while nitrogen gas was bubbled through themixture to substantially exclude oxygen (i.e., to a level wherepolymerization was no longer inhibited, i.e., about 1,000 parts permillion (ppm) or less). The mixture was irradiated with low intensityultraviolet light (e.g., “black light” having a wavelength of about 300nanometers to about 400 nanometers) until a viscous (i.e., having aviscosity of about 3,000 centipoise to about 5,000 centipoise),partially polymerized pre-adhesive composition was obtained.

The partially polymerized composition was knife-coated at a thickness ofabout 2.5 millimeters between two sheets of 50 micron-thick,ultraviolet-transparent, siliconized polyester film. The coated sandwichwas passed through two low intensity UV-irradiation zones, where a totalenergy of 750 milliJoules/cm² was expended. Zone 1 provided an energy ofapproximately 112.5 milliJoules/cm² and a light intensity of 0.8milliWatts/cm². Zone 2 provided an energy of approximately 637.5milliJoules/cm² and a light intensity of 2.0 milliWatts/cm². Duringirradiation, the coated sandwich was cooled by air impingement to removethe heat generated during polymerization. After passing through the twoexposure zones, the siliconized polyester sheets were removed from thesandwich to yield a solid acidic copolymer.

Acidic Copolymer C—(92/4/4 IOA/AA/SEA by wt. %) A 92/4/4 IOA/AA/SEAacidic copolymer was prepared by solution polymerization according tothe method of Acidic Copolymer A, except that 22.1 grams IOA, 1.0 gramAA, and 1.0 gram SEA were initially mixed along with the initiator,chain transfer agent, and reaction solvent.

Acidic Copolymer D—(95/4/1/IOA/AA/SEA by wt. %) A 95/4/1 IOA/AA/SEAacidic copolymer was prepared by solution polymerization according tothe method of Acidic Copolymer A, except that 22.8 grams IOA, 1.0 gramAA, and 0.2 gram SEA were initially mixed along with the initiator,chain transfer agent, and reaction solvent.

Acidic Copolymer E—(95/5 IOA/AA by wt. %) A 95/5 IOA/AA acidic copolymerwas prepared as follows. To a stainless steel reactor was added about517 parts of IOA, about 27 parts of AA, about 1 part of a 26.6% byweight solution of 4-acryloxy benzophenone (as prepared in Example A ofU.S. Pat. No. 4,737,559) dissolved in ethyl acetate, 0.00925 parts ofVAZO 52, 0.544 parts of IRGANOX 1010, and 0.272 parts of isooctylthioglycoate. The reaction mixture was purged with nitrogen for about 25minutes. Next, the reactor was pressurized to 68.9 kiloPascals (10 psig)with nitrogen. The reaction mixture temperature was set to about 63° C.(145° F.) and the mixture was agitated at 75 revolutions per minute(rpm). After the reaction began, the temperature increased adiabaticallyand peaked at about 143° C. (290° F.).

The mixture was cooled to about 54° C. (130° F.). Then, 0.0218 partsVAZO 52, 0.0435 parts VAZO 88, 0.0100 parts di t-butyl peroxide, 0.136parts isooctyl thioglycoate, 3.069 parts of a 26.6% by weight solutionof 4-acryloxy benzophenone (as prepared in Example A of U.S. Pat. No.4,737,559), and about parts of IOA were added to the reaction mixtureand mixed at about 75 rpm. The reactor was then pressurized to about137.9 kiloPascals (20 psig) with nitrogen. The reaction mixturetemperature was adjusted to about 63° C. (145° F.). After the reactionbegan, the temperature increased adiabatically and peaked at about 166°C. (330° F.). The reaction product was drained.

Acidic Copolymer F—(89/1.2/9.8 IOA/DMAEMA/AA by wt. %) A 89/1.2/9.8IOA/DMAEMA/AA acidic copolymer was prepared by solution polymerizationaccording to the method of Acidic Copolymer A, except that no chaintransfer agent was added.

Acidic Polymer G—(100 AA by wt. %) 5,000 weight average molecular weightpolyacrylic acid was used. This polymer is commercially available fromAldrich Chemical Company; Milwaukee, Wis., as 50% solids in water thatcan be dried prior to use.

BASIC POLYMERS

Basic Copolymer H—(80/10/10 DMAEMA/MMA/ODA by wt. %) To a stainlesssteel reactor was added about 92 parts of DMAEMA, about 12 parts of ODA,and about 12 parts of MMA. To this was added 0.0472 parts VAZO 52,0.0118 parts VAZO 67, and 0.236 parts IRGANOX 1010 dissolved in about0.9 parts of DMAEMA. The reaction mixture was purged with nitrogen forabout 20 minutes. The reactor was then pressurized to 206.8 kiloPascals(30 psig) with nitrogen. The reaction mixture temperature was set toabout 63° C. (145° F.) and the mixture was agitated at 75 rpm. Afterreaction began, the temperature increased adiabatically and peaked atabout 146° C. (295° F.).

The mixture was cooled to about 54° C. (130° F.). Then, 0.0472 partsVAZO 52, 0.0236 parts VAZO 67, and 0.0236 parts VAZO 88 dissolved inabout 1.4 parts of DMAEMA were added to the reaction mixture. Thereactor was pressurized to about 206.8 kiloPascals (30 psig) withnitrogen. The reaction mixture temperature was adjusted to 63° C. (145°F.) and the mixture was agitated at 75 rpm. After the reaction began,the temperature peaked adiabatically at about 161° C. (322° F.). Thereaction product was drained.

Basic Copolymer I—(90/10 IOA/DMAEMA by wt. %) A 90/10 IOA/DMAEMA basiccopolymer was prepared by solution polymerization according to themethod of Acidic Copolymer A, except that 21.6 grams IOA and 2.4 gramsDMAEMA were initially mixed along with the initiator and reactionsolvent. Also, no chain transfer agent was used.

Basic Copolymer J—(40/60 IOA/DMAEMA by wt. %) A 40/60 IOA/DMAEMA basiccopolymer was prepared by solution polymerization according to themethod of Acidic Copolymer A, except that 9.6 grams IOA and 14.4 gramsDMAEMA were initially mixed along with the initiator and reactionsolvent. Also, no chain transfer agent was used.

Basic Copolymer K—(40/60 ODA/DMAEMA by wt. %) A 40/60 ODA/DMAEMA basiccopolymer was prepared by solution polymerization according to themethod of Acidic Copolymer A, except that 9.6 grams ODA and 14.4 gramsDMAEMA were initially mixed along with the initiator and reactionsolvent. Also, no chain transfer agent was used.

Basic Copolymer L—(40/58/2 IOA/DMAEMA/AA by wt. %) A 40/58/2IOA/DMAEMA/AA basic copolymer was prepared by solution polymerizationaccording to the method of Acidic Copolymer A, except that 9.6 grams IOAand 13.9 grams DMAEMA and 0.5 gram AA were initially mixed along withthe initiator and reaction solvent. Also, no chain transfer agent wasused.

BLENDING AND APPLICATION METHODS

Hot-Melt Compounding and Coating (Method A)—The acidic polymer was fedinto a BONNOT extruder (available from Bonnot Co.; Uniontown Ohio),which was linked to an 18 millimeter diameter, co-rotating twin screwLEISTRITZ extruder having a 30:1 length:diameter ratio and six zones(available from Leistritz Corporation; Allendale, N.J.). Thetemperatures of the BONNOT extruder, melt pump, LEISTRITZ extruder anddie were set at 175° C. The acidic polymer was pumped into the firstzone of the LEISTRITZ extruder. The basic polymer was then fed into thesecond zone of the LEISTRITZ extruder using a K-TRON LOSS-IN-WEIGHTfeeder (available from K-Tron Corp.; Pitman, N.J.). The blend was thenhot-melt coated, using a rotary rod die onto a 38-micron-thick,polyester film backing (primed with an aminated polybutadiene) or onto asiliconized polyester release liner, as noted in the Examples following.Samples coated onto the siliconized polyester release liner were thenlaminated onto a polyester backing (primed with an aminatedpolybutadiene) for testing.

Batch Compounding/Hot-melt Coating (Method B)—The acidic polymer, basicpolymer, and optional tackifiers and plasticizers were blended in thestated ratios in a batch process at 1 50C. for 10 minutes using aBRABENDER PREP CENTER equipped with a 350-milliliter bowl mixer(available from C.W. Brabender Instruments, Inc.; South Hackensack,N.J.). The blend was then fed into a HAAKE single screw extruder(commercially available from Haake, Inc.; Paramus, N.J.) and hot-meltcoated, using a draw die, onto a polyester film backing (primed with anaminated polybutadiene).

Batch Compounding/Hot-melt Pressing (Method C)—The acidic polymer andbasic polymer were blended at 150° C. for 10 minutes in the ratiosstated below in a batch process using a BRABENDER PREP CENTER equippedwith a 30-milliliter bowl mixer (available from C.W. BrabenderInstruments, Inc.; South Hackensack, N.J.). The polymer blends were thenpressed between two standard, siliconized polyethylene terephthalaterelease liners at 150° C. and a pressure of about 138 MegaPascals(20,000 psi) using a CARVER hydraulic press, without shims, (availablefrom Carver, Inc.; Wabash, Ind.), such that a thin layer was formed. Thethickness of each sample varied from about 25 microns to about 150microns, with the actual thickness of each sample being indicated below.The pressed samples were then laminated to a 38-micron-thick, polyesterfilm backing, primed with an aminated polybutadiene, for peel adhesionand shear strength testing.

EXAMPLES Processed by Method A Examples 1-9 and Comparative Example C1

Blends of Acidic Copolymer A and Basic Copolymer H were compounded andcoated according to Method A in the relative amounts listed in Table 1.The coating thickness for each example is also listed in Table 1. Tapesamples for Examples 3, 6, 9, and C1 were hot-melt coated onto theprimed polyester backing, while tape samples for Examples 1, 2, 4, 5, 7and 8 were first hot-melt coated onto a siliconized release liner andthen laminated onto the primed polyester backing. The samples weretested according to the above shear strength methods. Tape samples 3, 6,and 9 were also tested for peel adhesion after being aged for one weekat a temperature of 23° C. and a relative humidity of 50%.

TABLE 1 Acidic Basic Copolymer A Copolymer H Peel (10% acidic (80% basicCoating Adhesion Shear monomers) monomers) Thickness (N/dm) Strength Ex.(parts) (parts) (microns) Initial Aged (min.) 1 100 0.8 38 33 — 527 2100 0.8 125 64 — 1,306 3 100 0.8 38 56 108 1,079 4 100 1.5 38 18 — 2,6875 100 1.5 125 22 — 5,982 6 100 1.5 38 26 77 6,124 7 100 2.9 38 2 —10,000+ 8 100 2.9 125 4 — 10,000+ 9 100 2.9 38 4 11 10,000+ C1 100 0 6377 — 27

Examples 1-9 show significant increases in shear strength of AcidicCopolymer A (cf., Comparative Example C1) due to the addition of minoramounts of the basic copolymer having a relatively high level of basiccomonomer. The shear strength results obtained are relativelyindependent of coating thickness. These results illustrate that adhesiveblends can be formulated to display a broad range of peel adhesion andshear strength properties.

Processed by Method B

Examples 10-11

Adhesive blends for Examples 10-11 were formulated according to theratios of Acidic Copolymer A, Basic Copolymer H, tackifier (ECR-180) andplasticizer (SANTICIZER 160) found in Table 2. The coating thickness foreach example is listed in Table 2. The tape samples were testedaccording to the above peel adhesion and shear strength methods.

TABLE 2 Acidic Copolymer A Basic Copolymer H Coating Peel Shear (10%acidic monomer) (80% basic monomer) Tackifier Plasticizer ThicknessAdhesion Strength Ex (parts) (parts) (parts) (parts) (microns) (N/dm)(min.) 10 100 2 15 5 150 18 6,444 11 100 1.5 0 0 150 13 4,802

Example 12 and Comparative Example C2

Adhesive blends for Examples 12 and C2 were formulated according to theratios of Acidic Copolymer A and Basic Copolymer K found in Table 3. Thecoating thickness for each Example is listed in Table 3. The tapesamples were tested according to the above peel adhesion and shearstrength methods.

TABLE 3 Acidic Basic Copolymer A Copolymer K (10% acidic (60% basicCoating Peel Shear monomer) monomer) Thickness Adhesion Strength Ex.(parts) (parts) (microns) (N/dm) (min.) 12 100 2 60 21 4,467 C2 100 0 5031 33

Processed by Method C Example 13 and Comparative Examples C3-C6

Blends were formulated according to the ratios of Acidic Copolymer A andBasic Copolymer I or H found in Table 5 and compounded and pressedaccording to Batch Compounding and Hot-melt Pressing Method C. Thecoating thickness for each example is also listed in Table 5. The tapesamples were tested according to the above peel adhesion and shearstrength methods.

TABLE 5 Acidic Basic Copolymer Copolymer A I (10% acidic (10% basicCoating Peel Shear monomer) monomer) Thickness Adhesion Strength Ex.(parts) (parts) (microns) (N/dm) (min.) C3 100 0 150 88 17 C4 100 10 5053 254 C5 100 20 63 59 464 C6 100 30 50 48 1,528 Basic Copolymer H (80%basic monomer) (parts) 13 100 1.5 38 57 10,000+

Examples 14-16 and Comparative Examples C7-C9

Blends were formulated according to the ratios of the Acidic Copolymer(C, D, or E) and Basic Copolymer (H) found in Table 6 and compounded andpressed according to Batch Compounding and Hot-melt Pressing Method C.The coating thickness for each example is also listed in Table 6. Thetape samples were tested according to the above peel adhesion and shearstrength methods.

TABLE 6 Basic Copolymer H Acidic (80% basic Coating Peel Shear Copolymermonomers) Thickness Adhesion Strength Ex. (100 parts) (parts) (microns)(N/dm) (min.) 14 C (8% acidic 2 125 53 1,832 monomers-4% AA, 4% SEA) C7C (8% acidic 0 50 81 87 monomers-4% AA, 4% SEA) 15 D (5% acidic 2 75 422,206 monomers-4% AA, 1% SEA) C8 D (5% acidic 0 100 99 11 monomers-4%AA, 1% SEA) 16 E (5% acidic 3.5 50 49 9 monomers-5% AA) C9 E (5% acidic0 55 85 1 monomers-5% AA)

Examples 17 and Comparative Example C10

Blends of Acidic Polymer G and Basic Copolymer J were hot-meltcompounded and coated according to Method C in the relative amountslisted in Table 7. The coating thickness for each sample is also listedin Table 7. The samples were tested according to the above shearstrength methods.

TABLE 7 Acidic Basic Polymer G Copolymer J (100% acidic (60% basicCoating Shear monomers) monomers) Thickness Strength Ex. (parts) (parts)(microns) (min.) 17 20 100 38 184 C10 0 100 38 5

As can be seen from Table 7, the addition of an acidic homopolymer to abasic copolymer can substantially increase the shear strength of thebasic copolymer.

Example 18 and Comparative Example C4

Blends of Acidic Polymer A and Basic Copolymer J were hot-meltcompounded and coated according to Method C in the relative amountslisted in Table 8. The coating thickness for each sample is also listedin Table 8. The samples were tested according to the above shearstrength methods.

TABLE 8 Basic Copolymer L Acidic (58% basic Polymer A (10% monomers; 2%Coating Shear acidic monomers) acidic monomers) Thickness Strength Ex(parts) (parts) (microns) (min.) 18 100 2 150 801 C4 100 0 150 17

As can be seen from Table 8, in blends of the present invention, one ofthe acidic or basic polymer can be a copolymer that is derived from bothacidic and basic monomers.

Example 19 and Comparative Example C11

For Example 19, a blend of Acidic Polymer A and Basic Copolymer J washot-melt compounded and coated according to Method C in the relativeamounts listed in Table 9. The coating thickness is also listed in Table9. The sample was tested according to the above shear strength method.

The proportionate amount of basic monomers in the polymer of ComparativeExample C11 is similar to that in the polymeric blend of Example 19.Similarly, the proportionate amount of acidic monomers in the polymer ofComparative Example C11 is similar to that in the polymeric blend ofExample 19.

TABLE 9 Basic Copolymer J Acidic (60% basic Coating Shear Polymermonomers) Thickness Strength Ex. (100 parts) (parts) (microns) (min.) 19A (10% acidic 2 150 10,000+ monomers) C11 F (9.8% acidic 0 125 182monomers; 1.2% basic monomers)

Example 20 and Comparative Example C12

In Example 20, an acidic polymer (Acidic Copolymer B) was blended with abasic polymer (Basic Copolymer H). The blends of Example 20 wereprocessed according to Method C in the relative amounts listed in Table10. The coating thickness for each sample is also listed in Table 10.The samples were tested according to the above peel adhesion and shearstrength methods.

TABLE 10 Acidic Copolymer B Basic Copolymer H Coating Peel Shear (10%acidic monomer) (80% basic monomer) Tackifier Plasticizer ThicknessAdhesion Strength Ex (parts) (parts) (parts) (parts) (microns) (N/dm)(min.) 20 100 1 15 5 100 94 10,000+ C12 100 0 0 0 90 103    97

Various modifications and alterations of the invention will becomeapparent to those skilled in the art without departing from the spiritand scope of the invention, which is defined by the accompanying claims.

What is claimed is:
 1. A hot-melt pressure-sensitive adhesivecomposition, comprising a blend of: an acidic copolymer derived from afirst group of monomers comprising at least one acidic monomer; and abasic copolymer derived from a second group of monomers comprising atleast one basic monomer, wherein at least one of the first and secondgroup of monomers comprises greater than 25% by weight of acidic orbasic monomers, respectively, and wherein one of the acidic copolymerand the basic copolymer comprises up to about 5% by weight of the blend.2. The composition of claim 1, wherein at least one of the first andsecond group of monomers comprises at least one (meth)acrylate monomer.3. The composition of claim 2, wherein each of the first and secondgroup of monomers comprises at least one (meth)acrylate monomer.
 4. Thecomposition of claim 2, wherein the (meth)acrylate monomer is an alkyl(meth)acrylate monomer.
 5. The composition of claim 1, wherein the firstgroup of monomers comprises at least one basic monomer.
 6. Thecomposition of claim 1, wherein the second group of monomers comprisesat least one acidic monomer.
 7. The composition of claim 1, wherein thefirst group of monomers is essentially free of basic monomers.
 8. Thecomposition of claim 1, wherein the second group of monomers isessentially free of acidic monomers.
 9. The composition of claim 1,wherein the acidic monomer is selected from the group consisting of anethylenically unsaturated carboxylic acid, an ethylenically unsaturatedsulfonic acid, an ethylenically unsaturated phosphonic acid, andmixtures thereof.
 10. The composition of claim 1, wherein the acidicmonomer is selected from the group consisting of an ethylenicallyunsaturated sulfonic acid, an ethylenically unsaturated phosphonic acid,and mixtures thereof.
 11. The composition of claim 1, wherein at leastone of the first and second group of monomers comprises greater thanabout 35% by weight of acidic or basic monomers, respectively.
 12. Thecomposition of claim 11, wherein at least one of the first and secondgroup of monomers comprises greater than about 50% by weight of acidicor basic monomers, respectively.
 13. The composition of claim 12,wherein at least one of the first and second group of monomers comprisesgreater than about 60% by weight of acidic or basic monomers,respectively.
 14. The composition of claim 1, wherein the basic monomeris a non-nucleophilic amine-functional monomer.
 15. The composition ofclaim 14, wherein the basic monomer has a formula:

wherein a is 0 or 1; R is selected from the group consisting of H— andCH₃—; X is selected from the group consisting of —O— and —NH—; Y is adivalent linking group; and Am is a tertiary amine fragment.
 16. Thecomposition of claim 15, wherein Am is a group:

wherein R¹ and R² are independently selected from the group consistingof an alkyl group, an aryl group, a cycloalkyl group, and an arenylgroup.
 17. The composition of claim 16, wherein Am is selected from thegroup consisting of pyridinyl and imidazolyl.
 18. The composition ofclaim 15, wherein Y is selected from the group consisting of—(CH₂)_(n)—, wherein n represents an integer of 1 to 5; and divalentalkyl groups having internal linkages selected from the group consistingof ether linking groups, thioether linking groups, keto linking groups,urea linking groups, urethane linking groups, amido linking groups, andcombinations thereof.
 19. The composition of claim 1, wherein the basicmonomer is selected from the group consisting of N,N-dimethylaminopropylmethacrylamide (DMAPMAm), N,N-diethylaminopropyl methacrylamide(DEAPMAm), N,N-dimethylaminoethyl acrylate (DMAEA),N,N-diethylaminoethyl acrylate (DEAEA), N,N-dimethylaminopropyl acrylate(DMAPA), N,N-diethylaminopropyl acrylate (DEAPA), N,N-dimethylaminoethylmethacrylate (DMAEMA), N,N-diethylaminoethyl methacrylate (DEAEMA),N,N-dimethylaminoethyl acrylamide (DMAEAm), N,N-dimethylaminoethylmethacrylamide (DMAEMAm), N,N-diethylaminoethyl acrylamide (DEAEAm),N,N-diethylaminoethyl methacrylamide (DEAEMAm),4-(N,N-dimethylamino)-styrene (DMAS), 4-(N,N-diethylamino)-styrene(DEAS), N,N-dimethylaminoethyl vinyl ether (DMAEVE),N,N-diethylaminoethyl vinyl ether (DEAEVE), vinylpyridine,vinylimidazole, and mixtures thereof.
 20. The composition of claim 1,wherein at least one of the first and second group of monomers comprisesa vinyl monomer.
 21. The composition of claim 1, wherein the secondgroup of monomers comprises greater than 25% by weight of basicmonomers.
 22. The composition of claim 1, wherein one of the acidiccopolymer and the basic copolymer comprises about 0.5% by weight toabout 5% by weight of the blend.
 23. A substrate at least partiallycoated with the composition of claim
 1. 24. A tape comprising: a backinghaving a first and second side; and the composition of claim 1 coated onat least a portion of the first side of the backing and, optionally, onat least a portion of the second side of the backing.